CN1318545C - Oil dehydrator - Google Patents

Abstract

The present invention relates to a method and a device for removing dissociated and emulsified or dissolved water from low volatile liquid, such as oil. The low volatile liquid is removed through relevant fluid stream contacting one side of a semi-permeable film. The semi-permeable film divides a separation chamber into a material inlet side and a permeation side, the fluid stream is injected into the material inlet side, and the water is taken out from the permeation side. The permeation side of the separation chamber is kept under the low moisture pressure through the vacuum existence or the use of purge gas.

Description

Oil dehydrator

Background of invention

1. invention field

The present invention relates to lubricated and hydraulic industry on wide significance, is used for from oil in particular to a kind of, and more in general be the equipment and the method for from low volatility liquid, removing free, emulsive or dissolved water.

2. correlation technique discussion

Oil is used in lubricated and the hydraulic efficiency system.People generally believe, all have deleterious effects the operation of oil, the component in the system and the system of the existence of water in this system.As everyone knows, when the water pollution enters into lubricated or hydraulic efficiency system, may cause the oxidation of burn into oil, chemical abrasion, bearing fatigue life reduction and lubricity loss.These deleterious effects may be directly to be caused by the water that exists with free, emulsive or dissolved form.

Therefore, in order to make lubricated and hydraulic efficiency system has best performance, the someone has carried out effective trial and comes to remove from oil and anhydrate.Be used for comprising settling tank or storage tank except that equipment and the system of polluting of anhydrating, whizzer, suction strainer and vacuum hydro-extraction oil refiner.But as being about to discuss, these equipment have tangible limitation aspect water separation capability, processing ease, investment cost or the productive expense.

Settling tank is removed a large amount of " dissociating " water according to oil and the density and the gravity settling difference of water from oil.In order to remove " dissociating " water effectively, the residence time that settling tank need be grown and huge floor space.But they are inoperative and can not remove dissolved water for the separating oil water miscible liquid.

Whizzer is by producing centrifugal force on fluid, promptly increase gravity effectively and quicken the gravity settling effect of W/O.Whizzer can be removed free-water effectively from oil.But these whizzers as a rule are very expensive, and limited in one's ability aspect the separating oil water miscible liquid.They can not remove dissolved water from oil.

The suction strainer uses special filtration medium, and this filtration medium can absorb the moisture in the oil.When suction, media expansion, constricted flow, the pressure reduction of strainer both sides raises.When pressure reduction reaches predetermined level, shift out and abandon this suction strainer, new strainer is installed.These suction strainers can be removed free-water effectively, but but effect is limited when removing emulsive or dissolved water from oil.In addition, the water-retaining capacity of suction strainer is limited.Therefore, expired water, just they must have been changed in case soak.Therefore, they only are used for wherein only existing the occasion of trace water usually.In the higher application scenario of the concentration of water, the cost of continuously changing the suction strainer just becomes very high.

There is the vacuum hydro-extraction oil refiner of several types to be used for oily dehydration.These oil refiners are operated to dry air or according to the combination of these two kinds of principles from oily mass transfer according to vacuum distilling, moisture usually.

In vacuum distilling, use the boiling point that vacuum reduces water.For example, at 1013mmH ₂O (29.92 " Hg) gauge pressure (standard atmospheric pressure) boiling point of water down is 100 ℃ (212_), but at 100mmH ₂O (about 26 " Hg vacuum condition) its boiling point of following time only is 50 ℃ (122_).By be suitable for sufficient vacuum with respect to the oil temperature, the water in the oil just will be evaporated to from oil in the low-pressure air (vacuum), thereby makes the oil dehydration.

Oil being flow to apply in the contactor of vacuum by vacuum pump is the typical method of realizing this operation.For the vaporization rate that makes water reaches the highest in given container, preferred oil has big surface-to-volume ratio.This can realize by making oil flow through the known additive method of structured packing, random packing, cascade tower tray, rotating-disk or vacuum distilling and contactor field.Oil enters at the top of contactor usually and is downward through filler by action of gravity, is extended to the film of relative thin.Collect described oil in the bottom of container, there, must it be discharged by oil pump.The example is referring to people's such as the United States Patent (USP) 4,604,109 of Koslow and Lundquist United States Patent (USP) 5,133,880.In order to reduce required vacuum tightness, can heat oil.

The purpose of using vacuum is to reduce the boiling point of water and improve dehydration rate.Also can heat and improve dehydration rate.But, must extreme care avoiding applying too many heat and/or too low vacuum because when temperature and/or vacuum are increased to its degree below boiling point, in the oil more and more low molecular weight hydrocarbon also will be evaporated.Should be appreciated that the liquid that any boiling point is lower than water also will be removed.According to different application scenarios, this may be wish or may not be desirable yet.

System based on mass transfer uses similar contactor.But it is not to rely on distillation to remove to anhydrate, but make dry air or gas continuously adverse current be upward through the oil that flows downward.Water molecules in the oil will be transferred in the air of relatively dry by concentration gradient.From contactor, extract the air that this moment moisturizes out and be discharged in the atmosphere by vacuum pump or gas blower.Needn't oil be heated to more than the boiling point of water in order to evaporate the water.Therefore, system compares with vacuum distilling, can use less heat and/or vacuum in order to mass transfer for system's dehydration on basis.

Though vacuum distilling and mass transfer system can remove free, emulsive and dissolved water really, their some defectives have hindered their widespread use.In these two systems, oil pump is done to be changeed, and use tank level control in container.Use tank level control can also guarantee that oil level does not become too high to avoid being full of oil in the vacuum vessel.This will reduce the dewatering efficiency of container or make container lose water separation capability, and even may cause oil to be full of container fully and overflow in the vacuum pump.

When water evaporated in oil, vacuum cleaner also was vulnerable to the influence of foaming phenomenon in the container.This foam is lower than the proportion of oil, and may cause the malfunctioning and cleaner performance reduction of tank level control.

Since use well heater, control piece, the ins and outs of pump etc., and cleaner is the equipment unit of relative complex.In addition, filler type, oil viscosity and the airflow rate of use are also limiting the flow velocity by contactor.This causes using very large container with respect to the fluidic amount usually.When the oil pump that is necessary, vacuum pump, well heater, control piece, switchboard and web member fitted together, it is very huge and expensive that system becomes.Because the part count and the complicacy thereof of these systems, the maintenance and operation cost of system is general also very high.

Because the vacuum hydro-extraction oil refiner has the ability of removing free, emulsive or dissolved water from oil, so the vacuum hydro-extraction oil refiner has become the needed method of dehydration from oil.But, the defective relevant with the oil vacuum cleaning device hindered being extensive use of of these cleaners and/or make they in major part the use in the lubricated or hydraulic efficiency system unrealistic.Because they have large-scale relatively size and cost, so they are limited in the non-moving fixation application occasion, and the use on mobile unit is unpractical.

Because their investment cost is very high, therefore, they can for good and all be installed in the system usually, unless this system is big relatively, expensive lubricated or hydraulic efficiency system.But they are shared by several systems usually, on a machine or storage tank, after the purifying oil, it is moved on another machine, or the like.But when cleaner used by this way, the oil that is not connected in the machine on the cleaner may be polluted by water.This oil will keep pollutional condition can make the oil dehydration coupled again and once more up to cleaner.Therefore, those skilled in the art are continuing to search better method always and remove from oil and anhydrate.The applicant attempts pointing to the film based system with it.

The film based system has been used for from organic system except that anhydrating.But it must be admitted that, and the film that is used for this purpose exists hole or defective, and this will make fluid press and be penetrated into per-meate side.This situation will be made olefiant loss.Also someone will consider to come the per-meate side of coated film, can make film silt and reduce the validity of its permeate water up like this with nonvolatile oil.

The United States Patent (USP) 4,857,081 of Taylor discloses a kind of hydrocarbon or halogenated hydrocarbon gas or liquid dehydration method of making.This method is based on the cuprammonium regenerated cellulose film, and the cuprammonium regenerated cellulose film is known for a person skilled in the art, and they have the structure (people's such as Isuge United States Patent (USP) 3,888,771) in interconnective passage or hole.These films also are considered to have about 10-90_, the pore distribution of average 30_ (people's such as Isuge United States Patent (USP) 3,888,771, the United States Patent (USP) 5,192,440 of Sengbusch).Dividing the mechanism of dried up institute foundation by this cuprammonium regenerated cellulose from liquid organic phase is dialysis mechanism.Permeate substance passes film with the form of liquid.Because porose on the film, so it allows to carry out hydraulic permeation by it.Water miscible material also can pass this film.This has just hindered its application aspect the dehydration of oil, and is certain water-soluble because oil also always has.

Even Taylor is suitable for the dehydration of oil, itself also will produce defective the structure of Taylor.The molecular structure of regenerated cellulose film is that the existence by moisture is kept.When hydrophilic film is removed moisture, aperture is subjected to big capillary tension, thereby may cause the film shrinkage cracking.Because film has the hole of various size, so the capillary tension that forms in drying process can cause producing stress-difference on the microtexture of whole film.As everyone knows, this stress-difference can produce crack or " defective " in film.If this film is used for making the closed system dehydration, the moisture in the film finally also will be removed so.Will form aforesaid crack or " defective " like this.At this moment, this " defective " will cause oil to be delivered to the opposite side of film under hydraulic pressure.

People's such as Pasternak United States Patent (USP) 5,182,022 discloses a kind of pervaporation method that is used for glycol dehydration.Ethylene glycol dissolves each other with water fully, but and it is characterized in that mixture wherein to be separated is the pervaporation application of complete miscibility.The sulfonated polyethylene resin molding that uses allows quite a large amount of ethylene glycol to see through.The infiltration that it will be apparent to those skilled in the art that so a large amount of ethylene glycol is owing to the hydraulic permeation by defective (referring to following definition), and described defective is present in (discriminating layer) in the separating layer.This invention does not need flawless separating layer, because admit of the loss of nonaqueous phase.But in the dehydration of the oil of lubricated and hydraulic efficiency system, situation but is not like this.

The United States Patent (USP) 5,464,540 of Friesen discloses a kind of method of removing a kind of component by pervaporation technology from the liquid raw material mixture.In people's such as Friesen patent, purge stream is made up of the component that will not be removed in the feedstream, and is incorporated in the module with the form of steam.Capable at the 5th hurdle 8-13, people such as Friesen propose, and this method can be used for making the oil dehydration such as sesame oil and Semen Maydis oil.But in the embodiment that this patent provides, people such as Friesen only provide and have been used to make the performance data of volatility far above the high volatile volatile organic compound dehydration of sesame oil and Semen Maydis oil.Particularly, Friesen provides the embodiment that makes acetone, toluene and ethanol dehydration.Therefore, obviously, Friesen fails to be familiar with and instructs needs to use flawless (as mentioned below) non-porous film make this class oil dehydration.Those skilled in the art also may be to providing the possibility statement into question of Semen Maydis oil or the logistics of sesame oil steaming out.

The United States Patent (USP) 5,552,023 of Zhou discloses a kind of membrane distillation method that is used for glycol dehydration.This method is used a kind of porous-film.This is unappealing for the dehydration of oil, because porous support might drench and make fluid owing to hydraulic action sees through.

People's such as Bratton United States Patent (USP) 6,001,257 discloses a kind of zeolite membrane that does not have defective basically that is used to make various liquid dehydrations.Capable pointed at the 4th hurdle 12-15 as Bratton, the use of zeolite membrane is very crucial for the function of equipment, because it can be used for separating any two kinds of liquid, wherein has only a kind of liquid can pass through zeolite membrane.Zeolite membrane is used zeolite type material (also claiming molecular sieve), include by Sauerstoffatom connect by channel network that silicon/the oxygen tetrahedron forms.The 2nd hurdle 46-49 capable showing, this material should " not have defective " basically, but does not define the degree of " basically " or the implied meaning of " defective ".This film can not be used to make the oil dehydration, is penetrated into per-meate side because the existence of defective as mentioned below will cause fluid to be pressed.

In the context of the present invention, the following term that uses in whole application is wanted to express with undefined implication:

Definition:

" defective " used herein is used for representing to allow low volatility liquid hydraulic permeation by the hole on the film with abundant size of this film.

Therefore " zero defect " do not represent that the restricted passage film carries out the substance channel of solution diffusion, do not allow the hole with abundant size of liquid hydraulic permeation by this film but do not comprise in the expression film.When the permanent hole that exists diameter more than or equal to the oil molecule size in the film (being pin hole), oil will tend to take place hydraulic permeation.Estimate that the molecular size of oil molecule is greater than the 5-10 dust, still, because oil is by the fractions consisting of differing molecular size, so accurate numerical value will depend on the chemical constitution of specific oil to be drained off.Therefore flawless film is limited to diameter than on the less hole of the molecular size of oil molecule.

" atresia " expression does not comprise the film in those holes that are commonly referred to as hole, described hole is meant the permanent hole of the molecular size that has oil molecule at least, as discussed above, estimate this hole greater than the 5-10 dust, but this depends on the particular type of oil to be drained off fully.

Though flawless film used herein must be an atresia, non-porous film used herein is zero defect not necessarily.In theory, non-porous film should be the film that does not have defective, does not promptly contain aforesaid defective.This is hinting that flawless film will have the ventilation property/selectivity identical with the dense film that is manufactured from the same material.But in fact, situation is not like this.For example, Pinnau and Koros (Pinnau, I. and Koros, W., " Gas-Permeation Properties ofAsymmetric Polycarbonate; Polyestercarbonate; andFluorinated Polyimide Membranes Prepared by the GeneralizedDry-Wet Phase Inversion Process ", J.Applied Polymer Science, the 46th volume, 1195-1204 (1992)) and Pesek (Pesek, S. " Aqueous QuenchedAsymmetric Polysulfone Flat Sheet and Hollow Fiber MembranesPrepared by Dry/Wet Phase Separation " submits to the paper (1993) of The Universityof Texasat Austin) flawless gas separation membrane is defined as the film of its selective permeability (perselectivity) for the 75%-85% of dense film.This shows, selective permeability is that 85% film can comprise the defective that a lot of permission fluid are pressed infiltration.

The film that investigation selects layer to form by the polysulfones that is carried on the inappreciable minor structure of intensity.In the time of 35 ℃, the oxygen perviousness of polysulfones is 1.4 barrer (membrane handbook), O ₂/ N ₂Selectivity be 5.6.The thickness of investigating polysulfones selection layer is 700_.This thickness is the typical thickness of commercial membrane.Therefore, this selection layer will be 20GPU for the perviousness of oxygen, will be 3.57GPU for the perviousness of nitrogen.According to Pinnau and Koros (1992), if O ₂/ N ₂Selectivity be 85% of dense film, perhaps be 4.76 in this case, it is flawless that this polysulfone membrane will be considered to.Clearly, according to definition of the present invention, this film includes defective.If defective is enough little, then will be subjected to the domination of Knudsen diffusion by flowing of this defective.If defective is big, so, will be (or viscosity) of convection current and will obeys Hagen-Poiseuille law by flowing of this defective.Following table has been illustrated for 1 square metre polysulfones model will make O ₂/ N ₂Selectivity be the number of defects of 4.76 different size.

By selecting the Knudsen diffusion of defective in the layer
				Defective diameter (_)	25	50	100
Number of defects	1.22E+11	1.53E+10	1.91E+9
				Surface porosity factor (defect area/total area)	6.0E-7	3.0E-7	1.5E-7

By selecting the convection current of defective in the layer, applied pressure is 1psig
				Defective diameter (m)	0.5	1	2
Number of defects	39700	247	15
				Surface porosity factor (defect area/total area)	7.8E-10	1.9E-10	4.9E-11

The mean sizes of the listed defective of last table is big must be enough to make fluid press infiltration by defective and the model that makes the oil dehydration industrial infeasible.But for the application scenario such as gas delivery, the existence of defective only can reduce isolating efficient and can not cause described model can not implement industrial.

In theory, non-porous film should be the film that does not have defective, does not promptly contain aforesaid defective.But in fact, situation is not like this.As run in the practice and those skilled in the art recognized, the film that is considered to atresia will allow hydraulic permeation to certain degree, usually be enough to that its gas-selectively is played meter by the intrinsic selectivity of dense film and be reduced to, and will still be considered to non-porous film up to 85%.Therefore, in fact this film will have hole relatively little but that number is still considerable.The actual number in acceptable hole is with the size in hole and to treat to be undertaken by this film the characteristic of isolating material relevant in " atresia " film.Flawless film used herein refers to the non-porous film that above is defined as atresia, rather than the defined non-porous film of term usually used in this field " atresia ".In order successfully to implement the present invention, described film must be as the term that defines among the present invention described " atresia " and " not having defective ".

" oil " is used for representing the low volatility chemical substance.Usually, oil will comprise the cut that is form of mixtures of many different molecular weights and molecular structure.

" semi permeable " however expression allows some material osmosis but not allow the film of other mass transfer.This film can also be called difference film (discerning membrane).

The expansion from the teeth outwards of " wetting " express liquid.

" silt " expression up by undesirable effect, filled the porous minor structure of film, perhaps oilyly applied the purging side of film and increased resistance to mass transfer such as oil.

Summary of the invention

The invention provides a kind of film based method that is used for removing free, emulsive or dissolved water from oily or other low volatility liquid.This method can be used to be in the mobile unit of operation and active state, and in fixed equipment and the technology.Described method simple to operate, equipment is little and compact simultaneously, and this makes its practical and all economical for the system of all sizes.

The present invention also provides a kind of flawless differentiation layer or film, and it does not allow liquid to carry out hydraulic permeation by it, has limited by distinguishing the osmosis of layer transmission.The present invention also provides penetrating district's removing of carrying out of stratified steam.Therefore, the invention provides and be used for more effectively from equipment and method the oil separated free, emulsive and dissolved water.

Specifically, the present invention relates to from oil, remove the method for anhydrating selectively with film atresia, flawless.More particularly, described method comprises by making oil remove from relevant oil stream and anhydrate with a side (" the feeding side ") contact of semi-permeable membranes.Described film is divided into feeding side that oil injects to the separate chamber and from wherein removing the per-meate side of water.Per-meate side is by the existence of vacuum or by using sweep gas to remain under the low water partial pressure.Water in the oil can be solubilized form, perhaps is to separate the phase form, or emulsive, dispersive or " free ".Mould material is a kind ofly to have a suitable chemical compatibility with oil, can allow water selectively through the material of its transmission simultaneously again.Film and oiling learn compatible be meant it not with the biochemical reaction of fry dried food ingredients, perhaps its physicals can not affect adversely when contacting with oil such as size, intensity, perviousness and selectivity.

Therefore, an object of the present invention is to overcome the shortcoming of conventional oily dewatering, and provide a kind of and new can overcome these circumscribed oily dehydration and equipment and methods of being used for.

Another object of the present invention provides a kind of oil dehydrator of removing free, emulsive or dissolved water from oil.

A further object of the present invention provides a kind of oil dehydrator easy and simple to handle.

A further object of the present invention provides a kind of relatively little and compact oil dehydrator.

A further object of the present invention provides a kind of economical oil dehydrator.

A further object of the present invention provides a kind of oil dehydrator of practicality in big mini system.

A further object of the present invention provides a kind of oil dehydrator that can be used on the mobile unit that is in operation and active state.

Become the accompanying drawing of a specification sheets part by reference group, will apparent other purpose of the present invention and advantage from the following description book and additional claim, wherein in some views, similarly quotation mark is represented corresponding parts.

The accompanying drawing summary

Fig. 1 is the skeleton view that is used for membrane structure of the present invention.

Fig. 2 is the skeleton view that can be used for the improvement project of film of the present invention.

Fig. 3 is the skeleton view that can be used for the another kind of improvement project of film of the present invention.

Fig. 4 A is the orthographic plan that is made into many hollow-fibre membranes of cushion as shown in Figure 3.

Fig. 4 B is the cross-sectional view of being got in the direction of arrows along Fig. 4 A section line B-B.

Fig. 4 C is the sketch of the pad shown in Fig. 4 B behind spiral wound.

Fig. 4 D is the skeleton view of two kinds of hollowfibre semi-permeable membrance structures after helically is reeled as shown in Figure 3.

Fig. 5 is the sketch of structure behind spiral wound shown in Figure 1.

Fig. 6 specifies exemplary membrane separation process sketch of the present invention, wherein removes by vacuum pump and anhydrates.

Fig. 7 is the improvement project sketch of separating technology shown in Figure 6, and wherein water is removed by gaseous purge stream.

Fig. 8 is the sketch of the another kind of improvement project of separating technology shown in Figure 6, wherein makes film avoid being subjected to the pollution of impurity in the feedstream by upstream filter.

Fig. 9 is the front view that specifies the tubular fibre film device of structure of the present invention, and wherein raw material flows in the hole of fiber.

Figure 10 is the front view that specifies the tubular fibre film device of structure of the present invention, and wherein raw material is in the flows outside of fiber.

Figure 11 is the front view that specifies the tubular fibre film device of structure of the present invention, and wherein the raw material direction of discharging at the flows outside of fiber and water and oil is adverse current and is removed.Oil extracts by the perforation core.

Figure 12 is the front view that specifies the tubular fibre film device of structure of the present invention, and wherein water is removed by sweep gas.

Figure 13 is the skeleton view of the improvement project of structure shown in Figure 1, and wherein film has the top layer of global formation.

Figure 14 is the front view of the fragment end of structure shown in Figure 13.

Figure 15 is the skeleton view of the improvement project of structure shown in Figure 3, and wherein film has the top layer of global formation.

Figure 16 is the front view of the fragment end of structure shown in Figure 13.

Detailed Description Of The Invention

Should be appreciated that concrete equipment illustrated in accompanying drawing and the specification sheets hereinafter and technology all are exemplary embodiment of the inventive concept that defines in the accessory claim.Therefore, should not be considered to the qualification effect about the concrete size of disclosed embodiment among the present invention and other physicalies, unless claim is clearly given explanation in addition.

Before describing the preferred embodiments of the invention, the the Hand book of Industrial Membranes that the Membrane Hand book 3-15 page or leaf published by Van NostrandReinhold in 1992 and nineteen ninety-five are published, first version, the content of 56-61 page or leaf is in the introducing the present invention who rewrites fully.

According to the present invention, there are a kind of equipment and method to can be used for from the low volatility liquid of width variety type very, removing to distinctiveness water or other volatile solvents.Low volatility liquid is defined as the liquid of normal boiling point greater than the normal boiling point (100 ℃) of water.Therefore, water can be categorized as high-volatile liquid.It must be admitted that, and the component that can demonstrate low volatility under pure state may present nonideal performance under mixture state.This may be because, compare with the apparent rate of evaporation of estimating from the volatility of pure component, the component that comes from the mixture has due to the bigger apparent rate of evaporation.Preferably, the present invention relates to from oil to divide dried up.

More particularly, described oily dehydration method may further comprise the steps: make atresia, flawless semi-permeable membranes contact with the liquid stream that comprises oil and water at least, wherein film is divided into the feed side of material liquid mixture injection with the separate chamber and from wherein taking out the per-meate side of water; Keep the part chemical potential gradient of water so that make water according to qualifications from feeding side by described membrane permeation to per-meate side; Remove the water that has infiltrated from per-meate side; With the oil of removing by the feeding side of film after the dehydration.Term " chemical potential gradient " also can be called " active gradient " or " partial pressure gradient ".Term " partial pressure gradient " is interpreted as the water vapor pressure that means per-meate side and corresponding to the difference between the equilibrium water vapour pressure of the concentration of W/O.

Be used to make the equipment of oil dehydration to comprise to comprise at least container atresia, semi permeable, flawless film, described film the mode in the described container of being inserted into makes the inside with container be divided at least one charging side room and a permeate chamber; At least one is used for the inlet hole of feed chamber; At least one is used for the outlet opening of feed chamber; At least one is used for the outlet opening of permeate chamber.This equipment can make oil-water mixture flow into import, and at least with a side contacts of semi-permeable membranes; Keep the part chemical potential gradient of water so that make water according to qualifications from feeding side by described membrane permeation to per-meate side; Remove the water that has infiltrated by outlet opening from per-meate side; With remove oil after the dehydration by outlet opening from the feeding side of film.

Film can be any form or shape, as long as provide one to be suitable for isolating surface.Its common example comprises from film carrier, tubular fibre, composite material sheet and matrix material tubular fibre.Hollow-fibre membrane can tank filling in or otherwise place so that nominally fiber is parallel to each other.The fiber of matrix material hollow-fibre membrane or hollow-fibre membrane can helically be reeled or distortion.Perhaps, fiber also can be made into cushion.Under the situation that film is made up of fiber flat sheet material or pad, described sheet material or pad can helically be reeled.In addition, can there be interlayer to separate described sheet material or pad.

The film that uses to small part by thin, flawless, fine and close, atresia separating layer (term " separating layer " also can be called " top layer ") and bearing structure formation.In embodiment optionally, separating layer can be self-contained; But, implementing when of the present invention and do not requiring like this.To those skilled in the art, in separating layer, separating layer that is obviously fine and close, atresia can have defective.When this separating layer is used for divided gas flow or liquid mixture, may there be isolating transmission by these defectives.Be used in this separating layer under the situation of separating gas mixture, carry out according to " solution diffusion " principle, then undertaken by Knudsen diffusion by the transmission of defective by the transmission of this separating layer.Referring to Clausi, the paper " Formation and Characterization ofAsymmetric Polyimide Hollow Fiber Membranes for GasSeparation " (1998) that N submits to The University ofTexas at Austin.When this separating layer that contains defective is used for the separating liquid mixture, will no isolating hydraulic pressure transmission take place by these defectives.Hydraulic permeation by these defectives will cause the per-meate side of liquid infiltration to film.Though this no isolating being transmitted in some application scenario is acceptable, but can't accept in other application.

An example flawless, fine and close, the atresia separating layer is the solution casting dense film.These films are known for a person skilled in the art.Flawless, fine and close, atresia separating layer with the feasible dehydration rate of industry can be carried out solution casting by this film that must be enough to allow to produce the dehydration rate of hope to thin thickness and be prepared.The potential defective can be by asking in the usefulness that cross-linking step repeatedly applies the solution casting polymkeric substance and eliminates.

In the particular case of oil dehydration, oil will cause oil to lose from system by hydraulic permeation to per-meate side, cause this water trap to be not suitable for industry and will use, and will cause the per-meate side of film to be silted up.If separating layer is carried on the per-meate side, then the oil of hydraulic permeation will be by water transmission be produced resistance filling porous carrier and silt described film up.In addition, because oily unlikely evaporation, if perhaps evaporate, its evaporation will can be not faster than the speed of carrying out hydraulic permeation by defective, and therefore, the existence of defective will irreversibly be silted described film up and be reduced rate of water loss.In addition, if film is not flawless fully, then can be applied to purging agent that per-meate side blows away moisture just may be by this film and therefore be entrained in " cleaning " oil.This may produce foam in oil, be undesirable therefore.

Transmit and be based on " solution diffusion " mechanism by this flawless, fine and close, atresia separating layer.To those skilled in the art, term " solution diffusion " is interpreted as that meaning permeate substance is dissolved in the separating layer, and then by separating layer diffusion, desorb on the penetration fact of separating layer subsequently.Oil and water are present in the liquid phase on the film feeding side, and the material that permeates then moves on in steam or the gas phase from the penetration fact of separating layer.If separating layer comprises any defective, then will be by separating layer generation hydraulic permeation, thus cause liquid to be transferred to per-meate side.As mentioned above, this situation will make film silt up, and causes the loss of oil in the system, and the two all can produce industrial unfavorable product.

To those skilled in the art, pervaporation is interpreted as that meaning the liquid mixture that dissolves each other fully passes through separation fine and close, the atresia separating layer.In addition, pervaporation is appreciated that to meaning component and removes in per-meate side by the separating layer infiltration and as steam with limited speed.In addition, when pervaporation dewatered, under the defective situation of separating layer, the situation that nonaqueous phase hydraulic pressure is transferred to per-meate side was not very serious.This is because nonaqueous phase has high vapour pressure and is easy to evaporation.Here it is even for low volatility component, as ethylene glycol, when mixing with water, it also can demonstrate the reason of comparing the performance of significantly not expecting with pure component.

Porous-film is unsuitable such as those porous-films that are used for micro-filtration, ultrafiltration and dialysis, because the low volatility fluid will and silt film up through the hole.

That suitable film comprises is fine and close, non-porous polymer film or have the fine and close relatively separating layer or the asymmetric membrane on top layer on one or two surfaces of bearing structure.Fine and close non-porous film or prepare by " phase inversion " or by solution casting.Under the situation of phase inversion, polymkeric substance-solvent-nonsolvent system introduces non-solvent by evaporating solvent, extraction solvent or in system and is forced to precipitation.Phase inversion produces the porous polymer matrix of non-homogeneous, and it can be symmetric or can not be symmetric, and can have or can not have fine and close non-porous polymeric object area.Fine and close atresia separating layer can form by being separated by suitable selective solvent-non-solvent system and settling system.Under the situation of solution casting, it is dry then to make suitable polymkeric substance-solvent systems form gel.The homogeneous film that the solution casting polymkeric substance is normally non-porous.In both cases, Zhi Mi nonporous film all can form on another kind of bearing structure.The atresia separating layer of the densification that is formed by these two kinds of methods probably has defective (United States Patent (USP) 4,230,463).These separating layers are carried out aftertreatment also carried out reporting (Henis by Henis and Tripodi with the method that reduces defective basically, J. and Tripodi, M., " Composite Hollow Fiber Membranes for Gas Separation:TheResistance Model Approach ", J.Membr.Sci., (8), 233-245 (1981)).These methods that are used to reduce defective comprise and repeatedly apply defective film up to eliminating all defectives.Follow-up coating can be based on the identical polymkeric substance as original layers, perhaps based on different polymkeric substance.Flawless, fine and close, atresia separating layer can by solution casting fully thick homogeneity polymeric film form.Pfromm also illustrates, can form ultrafine, flawless, fine and close, atresia separating layer (Pfromm, P.H., " Gas transport properties and aging of thin and thick filmsmade from amorphous glassy polymers ", this is a paper (1994) of submitting to The Universityof Texas at Austin).

To those skilled in the art, gas is considered to " intrinsic " characteristic (Clausi, 1998) of polymkeric substance usually by the transport property of the atresia homogeneous polymers film of flawless densification.The intrinsic perviousness of polymkeric substance, for example and do not rely on the thickness of separating layer.If this separating layer is used for separating gas mixture, and this layer or film independently, or be in the matrix material of comparing with separating layer on the inappreciable carrier of transport resistance, then the perviousness ratio of actual mixt also is the natural characteristics of polymkeric substance under those actual conditionses.This ratio is known as the intrinsic selectivity of polymkeric substance for concrete gaseous fraction.

If fine and close, atresia separating layer does not show " intrinsic " selectivity for specific gaseous mixture, then this separating layer includes defective probably.This is because described defective allows component to be separated not have transmission discretely.When porous support provided inappreciable resistance to flow, those skilled in the art used this method to determine whether have defective (Clausi, 1998 in the separating layer usually; United States Patent (USP) 4,902,422).No matter separating layer forms according to what mechanism, this method all can be used for determining wherein whether to exist defective.If do not have defective in the proof separating layer, then it will can not allow gas or liquid not to have discretely to transmit, and under the situation of liquid infiltration, seeing through material will desorb from film with the form of steam.

That approach, fine and close, atresia separating layer can be a layer independently.Nominally it also can with bearing structure simultaneously and global formation.Its composition material can be with bearing structure identical, perhaps can form with the form of matrix material by different materials.There is a tight zone to be connected on the bearing structure on the composite membrane.After this fine and close, atresia separating layer can form as an independent step.These composite membranes, fiber or sheet material can be porous or atresia.Described sheet material is preferably flat, though implementing when of the present invention and do not requiring so.These fibers, film or sheet material can install on one or more sides so that feed chamber and permeate chamber are separated.Separating layer in this film can be identical with bearing structure or different, described bearing structure can be by porous organic or inorganic polymer, pottery or glass form.Embodiment preferred is to have thin, fine and close, atresia separating layer polymkeric substance composite sheet or matrix material tubular fibre in the one side of carrier or two sides.Under the situation of symmetry or asymmetric membrane, liquid can contact with film in any side, although embodiment preferred will be that the interfacial layer of feeding side is dropped to that minimum side.

Fine and close non-porous layer or top layer also can be an integral parts of film and form simultaneously with bearing structure at least on paper.But the present invention is not limited to bearing structure and forms fine and close non-porous layer simultaneously.The present invention also can be shaped to an integral part (a.k.a. composite part) of film by the non-porous layer with densification and implement.The formation of fine and close non-porous layer can be different with the formation time of bearing structure.In this case, Zhi Mi non-porous layer is connected on the bearing structure subsequently.

Bearing structure can be porous or atresia.Fine and close atresia top layer, perhaps bearing structure can have polymer property in nature.Fine and close atresia top layer, perhaps bearing structure can be inorganic or organic polymer.Described polymkeric substance can be a simple linear polymer, branched polymer, cross-linked polymer, ring-type simple linear polymer, ladder polymer, ring-type matrix polymer, multipolymer, terpolymer, graftomer, perhaps its blend.

Low volatility liquid may wetting porous bearing structure.Perhaps, can handle so that nonwetting this structure of low volatility liquid the porous bearing structure.But, implementing when of the present invention and do not requiring like this.When porous carrying not by low volatility liquid when wetting the present invention still can implement.In addition, when porous carrying is handled so that its not by low volatility liquid when wetting, the present invention also can implement.Preferably, the character of porous bearing structure makes nonwetting this structure of low volatility liquid.

Only under situation about forming by the non-porous layer or the top layer of densification on the side, exist defective will probably cause produce the passage of discussed above oil in the non-porous layer of densification at film.Therefore if oil carries out hydraulic permeation by film, then its vaporator rate might be lower than water, and perhaps evaporation can make film silt up and reduces rate of water loss.Therefore, embodiment preferred should be all to have flawless, fine and close atresia separating layer or top layer on porous bearing structure one side or both sides.It is very necessary having flawless, fine and close, atresia separating layer, can make the oil can not be by the defective generation hydraulic permeation in the separating layer like this.All having an advantage flawless, fine and close, the atresia separating layer in the both sides of vesicular structure is further to have reduced the possibility that oil carries out the hydraulic pressure transmission.

Under the situation of tubular fibre, raw material can contact with film in the hole of fiber or in the outside of fiber.It is outside so that the embodiment of lower operation pressure reduction to be provided that embodiment preferred should be that liquid is injected into.

Separating layer or top layer can be made up of the polymkeric substance of any type compatible with the raw material chemistry, as long as fine and close non-porous layer does not allow oil to transmit in large quantities.If separating layer or top layer not with the biochemical reaction of fry dried food ingredients, if perhaps its physicals such as the influence that size, intensity, perviousness and selectivity can not be subjected to and oil contact, thinks that then this separating layer or top layer and oiling is compatible.Fine and close non-porous layer can be made up of the following stated polymkeric substance, and it is including, but not limited to such as polyimide, polysulfones, and polycarbonate, polyester, polymeric amide, polyureas gathers (ether-amide) amorphous special teflon, poly organic silicon alkane, alkylcellulose and polyolefine.

Liquid can contact with film by adverse current and stream, cross-flow or radially cross-flow mode.Flow can so that one of them, not or two logistics all (that is, raw material and penetrant) mix well or do not mix.Feedstream is preferably mixed well.

Containing low volatility liquid (for example oil) and the liquid stream of water can be injected in the container to contact with the non-porous layer of the flawless densification of film.But operation of the present invention is not limited to liquid is injected in the container and contacts with the non-porous layer of densification.The present invention can also be by being injected into liquid in the container so that it is not having the fine and close non-porous layer or a side on top layer to contact with film.

The dividing potential drop of per-meate side water can reduce such as carbonic acid gas, argon gas, hydrogen, helium, nitrogen, methane or preferred air by using vacuum or using low steam partial pressure sweep gas.Permeate stream comprises that purging agent preferably is adverse current, cross-flow or radially cross-flow mode.The pressure of penetrant can be equal to or less than the pressure of raw material.

Perhaps, the pressure of penetrant can be greater than the pressure of raw material.Permeate pressure is the situation of removing penetrant by sweep gas greater than an example of feed pressure, and described sweep gas can be made up of the pressurized air or the nitrogen of dehydration, and the pressure of per-meate side is just greater than the pressure of container feeding side like this.The activity of the high volatile volatile liquid that from raw material, shifts out usually in this case, in subrange feeding side greater than per-meate side.

When using the dehydration of film base oil, preferably the supplied materials logistics is filtered.Filtration can be used for removing the big water gaging that particulate material or logistics are carried secretly.Any method that is used for filtered fluid known in the art all is fit to.This particulate matter that can prevent that separating layer from being carried secretly in this logistics damages.

In preferred embodiments, film, tubular fibre flawless, atresia separating layer fine and close by having on the one or both sides of porous bearing structure formed.In preferred embodiments, the feeding side interfacial layer is reduced to minimum.In addition, in preferred embodiments, the pressure reduction that passes feeding side is reduced to minimum.Can or purge agent by vacuum and take out the water that infiltrates from per-meate side.This water will be steam or gaseous state.Purging agent can be gas or liquid.In addition, purge agent for the activity of water can be than low volatility liquid low.

This equipment can be used for wherein using the situation of vacuum cleaner and other conventional water traps.This method or equipment can be used for handling the oil in " kidney shape loop " system, and wherein oil dehydrator is connected on the storage tank that belongs to an equipment part.Oil is taken out from the technology storage tank,, turn back in the storage tank then by water trap processing.Oil dehydrator can continuous or periodical operation when host system is in operation or stationary state.This equipment can also " off line " be operated the fluid of handling in the storage tank.This storage tank is free of attachment on any parts of operating equipment and as regulating the fluidic container.

Except the application of routine, this equipment can " online " use.Because charging and permeate chamber are separated by the atresia interlayer of densification, so can operate so that raw material is under the different pressure with penetrant to equipment.Therefore, this equipment can be operated in such a way, even oil is under the system pressure that wherein uses this oil.Therefore, this has just started the possibility of this equipment of online use and method, and this online use is the preferred embodiments of the invention.It reduces and even can eliminate for the off line of routine or the needs of kidney shape circuit system.Because the present invention can be online and be used under system pressure, so equipment of the present invention can be compacter, weight is lighter, and in fact can be used on all hydraulic pressure or lubrication fittings.Because do not need other power, pump and control piece, so it can also be used for fixing in formula or the mobile unit.

With reference now to accompanying drawing,, wherein similar numeral components identical, Fig. 1 is the flat sheet type embodiment of semi-permeable membranes 18.Film 18 comprises separating layer atresia, flawless or top layer 22 and bearing structure 24.Separating layer or top layer 22 may reside in a side or the both sides of bearing structure 24.

About Figure 13-14, shown an improvement project of semi-permeable membranes 18, wherein separating layer or top layer 22 are by known method in film field and bearing structure 24 global formations.As previously mentioned, separating layer or top layer 22 may reside in a side or the both sides of bearing structure 24.

In Fig. 2, two plain film shape semi-permeable membraness 18 are separated by many feeding-passage sealing coats 34.Sealing coat 34 can be by various materials well known in the art, comprise that sealing agent makes or form.Each film 18 all has top layer 22 and bearing structure 24.Be used for preventing that raw material and permeate stream blended permeate collection sealing coat 25 are inserted between film 18 and the sealing coat 34.Film 18 is fed channel separation layer 34 and separates.

What describe in Fig. 3 is the tubular fibre embodiment of semi-permeable membranes 20.In this embodiment, hollow-fibre membrane 20 comprises separating layer 22 and bearing structure 24.Described separating layer can be in the inboard of fiber or the outside or in its both sides.

About Figure 15-16, shown an improvement project of hollow-fibre membrane 20, wherein separating layer or top layer 22 are by known method in film field and bearing structure 24 global formations.As previously mentioned, separating layer or top layer 22 may reside in a side or the both sides of bearing structure 24.

Shown in Fig. 4 A is a plurality of hollowfibre semi-permeable membrances 20 that are made into pad 30.According to weaving or net-forming process, hollow-fibre membrane 20 will form the latitude portion of cushion fabric 30 usually.Many weighting materials 28 are used for hollow-fibre membrane 20 is woven into pad.Weighting material 28 uses in the mode of traditional textile mat or net.

The cross-sectional view of section line B-B in Fig. 4 A is shown among Fig. 4 B.Reference signs of using among Fig. 4 B and previous sign are represented components identical.Only otherwise damaged fiber, any weaving type method all can be used for forming hollow fiber mat.

In Fig. 4 C, pad 30 is by spiral wound.Usually, feeding-passage sealing coat 34 such as sealing agent 35, applies the end that is close to pad 30, and will fill the space between the tubular fibre 20, and is such as will be further discussed.

In Fig. 4 D, two hollowfibre semi-permeable membrances 20 are reeled by helically and are formed " rope " 32.

In Fig. 5, use known screw winding structure and method with plain film shape semi-permeable membranes 18 screw windings, feed chamber and permeate chamber just are provided in the spiral wound model like this.Before film 18 is carried out screw winding, feeding-passage sealing coat 34 is placed on the separating layer 22.The more than one plain film shape of screw winding semi-permeable membranes 20 simultaneously.Usually, a plurality of plain film shape semi-permeable membraness 18 will be horizontally disposed each other.Film 18 can be separated by sealing coat 34 or can be not separated.Then, with the subassembly of horizontally disposed a plurality of flat sheet membranes 20 around core 60 (if you are using) screw winding.Usually, spiral should tightly be reeled, and feeding-passage sealing coat 34 will contact infiltration collection sealing coat 25.

In Fig. 6, the present invention with vacuum infiltration pattern has been described.Water-containing material 40 is introduced in the feeding side of membrane separation apparatus container 42, thereby oil is effectively contacted with film 18, is beginning with before film 20 contacts, and raw material 40 can optionally heating.Low volatility liquid after the dehydration shifts out from container 42 with the form of ejecta 44.Penetrant 46 takes out by vacuum pump 48.Optional, raw material 40 can be parallel or be flowed perpendicular to film 20, penetrant 46 also can be parallel or perpendicular to film 20 or its arbitrarily array mode flow.Optional, container 42 can be heated.

Obviously, the size of container 42 should suitably design with the amount with the operation pressure reduction of the flow velocity of the raw material 40 of hope, hope and water to be removed and be complementary.Illustrational penetrant 46 is the cross-flow form, still, raw material 40 and penetrant 46 also can be each other adverse current, and stream or radially cross-flow mode flow.

Fig. 7 and 8 illustrated the sweep gas pattern, wherein on the per-meate side of film 20, have an import that is used for purge stream 50.Feedstream can filter by strainer 52 as shown in Figure 8.

At Fig. 9, in 10,11 and 12, the fluid of tubular fibre 20 hole sides comes by sealing agent 34 and fluid separation in the shell-side.In Figure 11, oil is discharged by perforation core 60.Perforation core 60 is conventional perforation cores, and it has a shell 62, and the part 64 and the outlet 68 of perforation are arranged on the shell.The part of perforation comprises many perforates 66.Outlet 68 is connected with the ejecta 44 of container 42.Perforate can have any suitable size or structure.The low volatility liquid flow is crossed shell 62 and perforated portion 64.Low volatility liquid enters into shell 62 by perforate 66.Low volatility liquid is discharged perforation core 60 by outlet 68.

Except lubricating oil, this equipment and method can also be used to make other fluid dehydration, such as plant or food-grade oil, and siloxanes, perhaps other low volatility fluid.

Be used for the term of specification sheets above and wording as an illustration the property term use, and do not play the qualification effect, when using this term and wording, do not want to get rid of the Equivalent of shown or the feature described or the part of Equivalent.Admit that scope of the present invention is only given definition and restriction by following claim.

Claims (87)

1. one kind makes oily dehydration method, may further comprise the steps:

A) side that makes flawless, fine and close non-porous film contact with the liquid stream that contains free, emulsive or dissolved water and oil, and wherein said film is divided into the feeding side of liquid stream injection with the separate chamber and from wherein taking out the per-meate side of water; Wherein:

1) flawless, fine and close non-porous film is the composite part of tubular fibre, and wherein flawless, fine and close, atresia separating layer loads on the porous support; With

2) separating layer and porous support are polymer properties in nature;

B) keep partial pressure difference for water so that water penetrates the polymkeric substance separating layer by " solution diffusion " from feeding side selectively, be penetrated into per-meate side with the form of steam;

C) remove the water vapor that has infiltrated from per-meate side with gaseous purge stream or vacuum;

D) prevent that oil is penetrated into per-meate side with liquid form; With

E) remove oil after the dehydration from the feeding side of film.

2. one kind makes low volatility liquid dehydration method, may further comprise the steps:

A) side of the semi-permeable membranes of flawless, atresia contact with the liquid stream that contains water and low volatility liquid at least, wherein said film is divided into the feeding side of liquid stream injection with the separate chamber and from wherein taking out the per-meate side of water, wherein:

1) flawless, fine and close non-porous film is the composite part of tubular fibre, and wherein flawless, fine and close, atresia separating layer loads on the porous support; With

2) separating layer and porous support are polymer properties in nature;

B) so that water is penetrated into per-meate side by described film from feeding side, low volatility liquid then can not be penetrated into per-meate side by the hydraulic pressure type of transmission for the partial pressure difference of water in maintenance;

C) remove the water that has infiltrated from per-meate side; With

D) remove liquid after the dehydration from the feeding side of film.

In the claim 2 definition method, wherein low volatility liquid be oil.

In the claim 2 definition method, wherein low volatility liquid is defined as the liquid of its normal boiling point greater than the normal boiling point of water.

5. the method for definition in the claim 2, wherein water is present in the low volatility liquid mutually with the form of dissolved, dispersive or emulsive or with free.

6. the method for definition in the claim 2, the semi-permeable membranes of wherein flawless, atresia by densification, the forming of atresia from carrier layer.

7. the method for definition in the claim 2, wherein liquid stream is mixed well.

8. the method for definition in the claim 2, wherein liquid stream mixes well.

In the claim 2 definition method, wherein this method is in another system online, in described another system, at least a portion of low volatility liquid total flux charging constantly during described method is carried out.

In the claim 2 definition method, wherein this method is operated in " kidney shape loop " mode in another system, in described another system, the charging constantly during described method is carried out of the part of low volatility liquid total flux.

11. the method for definition in the claim 2, wherein this method is operated with off line mode in another system, and wherein, low volatility liquid charging from storing device during described method is carried out.

12. the method for definition in the claim 2, wherein the raw material flow direction is parallel with the semi-permeable membranes surface.

13. the method for definition, wherein raw material flow direction and semi-permeable membranes Surface Vertical in the claim 2.

14. the method for definition in the claim 12, wherein mobile the and semi-permeable membranes of per-meate side is surperficial parallel.

15. the method for definition in the claim 12, the wherein Surface Vertical of the mobile and semi-permeable membranes of per-meate side.

16. the method for definition in the claim 13, wherein mobile the and semi-permeable membranes of per-meate side is surperficial parallel.

17. the method for definition in the claim 13, the wherein Surface Vertical of the mobile and semi-permeable membranes of per-meate side.

18. the method for definition, the wherein mobile reflux type that is of feeding side and per-meate side in the claim 2.

19. the method for definition in the claim 2, wherein the mobile of feeding side and per-meate side is and stream mode.

20. the method for definition, the wherein mobile cross-flow mode that is of feeding side and per-meate side in the claim 2.

21. the method for definition, the wherein mobile radially cross-flow mode that is of feeding side and per-meate side in the claim 2.

22. the method for definition in the claim 2, wherein the pressure of per-meate side is greater than the pressure of feeding side.

23. the method for definition in the claim 2, wherein the pressure of per-meate side equates with the pressure of feeding side or is lower than it.

24. the method for definition wherein has sweeping gas or liquid to pass through per-meate side in the claim 2.

25. the method for definition wherein have sweeping gas to pass through per-meate side, and described sweep gas is selected from argon gas, methane, nitrogen, air, carbonic acid gas, helium, hydrogen or its any mixture in the claim 2.

26. the method for definition wherein has sweep gas to pass through per-meate side in the claim 2, and described sweep gas active low for the specific activity low volatility liquid of water.

27. the method for definition in the claim 2, wherein porous support is a pottery.

28. the method for definition in the claim 2, wherein porous support is a glass.

29. the method for definition in the claim 2, wherein porous support is an inorganic polymer.

30. the method for definition in the claim 2, wherein low volatility liquid be filtered before semi-permeable membranes contacts.

31. the method for definition in the claim 2, wherein semi-permeable membranes is made up of many tubular fibres, and tubular fibre is woven into cushion.

32. the method for definition in the claim 2, wherein liquid stream be heated before film contacts.

33. the method for definition in the claim 2, the semi-permeable membranes of wherein said atresia has the top layer of global formation at least one side of bearing structure.

34. one kind makes oily dehydration method, may further comprise the steps:

A) side flawless, semi permeable non-porous film is contacted with the liquid stream that contains water and oil at least;

B) wherein water is present in the oil with free, emulsive or dissolved form;

C) wherein said film is divided into feeding side that liquid stream injects with the separate chamber and from wherein taking out the per-meate side of water;

D) so that water is penetrated into per-meate side by described film from feeding side, oil then can not be penetrated into per-meate side by the hydraulic pressure type of transmission for the partial pressure difference of water in maintenance;

E) remove the water that has infiltrated from per-meate side; With

F) remove oil after the dehydration from the feeding side of film.

35. the method for definition in the claim 34, the semi-permeable membranes of wherein flawless, atresia is made up of the non-porous layer of the densification on one or more tubular fibres that are in porous or atresia.

36. the method for definition in the claim 34, the semi-permeable membranes of wherein flawless, atresia is made up of the non-porous layer of the densification on one or more flat sheet materials that are in porous or atresia.

37. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the non-porous layer as the densification of tubular fibre inalienable part, and the non-porous layer of described densification and the bearing structure in the tubular fibre form simultaneously.

38. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the non-porous layer as the densification of flat sheet material inalienable part, nominally the non-porous layer of described densification and the bearing structure in the flat sheet material form simultaneously.

39. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the non-porous layer as the densification of composite part inalienable part, and the bearing structure in the non-porous layer of described densification and the tubular fibre is in different time formation.

40. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the non-porous layer as the densification of flat sheet material inalienable part, and the bearing structure in the non-porous layer of described densification and the flat sheet material is in different time formation.

41. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the bearing structure of tubular fibre form, and described tubular fibre has fine and close non-porous layer on hole or outside surface.

42. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the bearing structure of flat sheet form, has fine and close non-porous layer on the side of described flat sheet material.

43. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the bearing structure of tubular fibre form, and described tubular fibre has fine and close non-porous layer simultaneously on hole and outside surface.

44. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the bearing structure of flat sheet form, has fine and close non-porous layer on the both sides of described flat sheet material simultaneously.

45. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on the tubular fibre that is in porous or atresia, and the low volatility liquid feeding is to the side with fine and close non-porous layer.

46. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on the flat sheet material that is in porous or atresia, and oil is fed to a side that does not have fine and close non-porous layer.

47. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more tubular fibres that are in porous or atresia, the wherein oily outside that is fed to fiber.

48. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more tubular fibres that are in porous or atresia, the wherein oily inboard that is fed to fiber.

49. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more tubular fibres that are in porous or atresia, wherein said fiber helically coiling.

50. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more flat sheet materials that are in porous or atresia, wherein said flat sheet material helically coiling.

51. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more flat sheet materials that are in porous or atresia, wherein sealing coat separation flat sheet material.

52. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more tubular fibres that are in porous or atresia, and raw material is mobile with the direction that is parallel to tubular fibre.

53. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer that at least one is in the densification on the tubular fibre of porous or atresia, and at the mobile tubular fibre that is parallel to of per-meate side.

54. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer that at least one is in the densification on the tubular fibre of porous or atresia, and mobile perpendicular to tubular fibre in per-meate side.

55. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer that at least one is in the densification on the tubular fibre of porous or atresia, and raw material is mobile with the direction perpendicular to tubular fibre.

56. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer that at least one is in the densification on the flat sheet material of porous or atresia, and raw material is mobile with the direction that is parallel to flat sheet material.

57. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer that at least one is in the densification on the flat sheet material of porous or atresia, and at the mobile flat sheet material that is parallel to of per-meate side.

58. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer that at least one is in the densification on the flat sheet material of porous or atresia, and mobile perpendicular to flat sheet material in per-meate side.

59. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer that at least one is in the densification on the flat sheet material of porous or atresia, and raw material is mobile with the direction perpendicular to flat sheet material.

60. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the porous bearing structure, and the porous bearing structure is wetting by low volatility liquid.

61. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the porous bearing structure, and the porous bearing structure is handled so that it is wetting by low volatility liquid.

62. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the porous bearing structure, and the porous bearing structure is not wetting by low volatility liquid.

63. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises the porous bearing structure, and the porous bearing structure is handled so that it is not wetting by low volatility liquid.

64. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises fine and close non-porous layer, and described non-porous layer is a polymer property in nature.

65. the method for definition in the claim 34, wherein the semi-permeable membranes of flawless atresia comprises fine and close porous support, and the porous support of described densification is a polymer property in nature.

66. the method for definition in the claim 34, wherein the semi-permeable membranes of uniform texture is made up of from carrier layer the atresia of the densification with global formation top layer.

67. an equipment that is used to make the oil dehydration comprises:

A) dress fluidic container;

B) be inserted into the semi-permeable membranes that in the described container inside of described container is divided into the flawless atresia of at least one feed chamber and a permeate chamber;

C) at least one is used for the inlet hole in charging side room;

D) at least one is used for the outlet opening in charging side room; With

E) at least one is used for the outlet opening of permeate chamber;

68., also comprise the porous support of the semi-permeable membranes that is used for the described atresia of load according to the equipment of claim 67.

69. according to the equipment of claim 68, the semi-permeable membranes of wherein said atresia has the top layer of global formation at least one side of porous support.

70. according to the equipment of claim 67, the semi-permeable membranes of wherein said atresia is a polymer property in nature.

71. according to the equipment of claim 68, wherein said porous support is a polymer property in nature.

72. according to the equipment of claim 68, wherein said porous support is a pottery.

73., also comprise the sweep gas import that is used for permeate chamber according to the equipment of claim 67.

74. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia is made up of from carrier layer the atresia of densification.

75. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more tubular fibres that are in porous or atresia.

76. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more flat sheet materials that are in porous or atresia.

77. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia comprises the non-porous layer as the densification of tubular fibre inalienable part, the non-porous layer of described densification and the bearing structure in the tubular fibre form simultaneously.

78. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia comprises the non-porous layer as the densification of flat sheet material inalienable part, nominally the non-porous layer of described densification and the bearing structure in the flat sheet material form simultaneously.

79. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia comprises the non-porous layer as the densification of composite hollow fiber parts, the bearing structure in the non-porous layer of described densification and the tubular fibre formed in the different time.

80. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia comprises the non-porous layer as the densification of flat sheet material composite part, the bearing structure in the non-porous layer of described densification and the flat sheet material formed in the different time.

81. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia comprises the bearing structure of tubular fibre form, described tubular fibre has fine and close non-porous layer on hole and outside surface.

82. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia comprises the bearing structure of flat sheet form, has fine and close non-porous layer at least one side of described flat sheet material.

83. equipment according to claim 67, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on the tubular fibre that is in porous or atresia, and the low volatility liquid feeding is to the side with fine and close non-porous layer or there is not a side of fine and close non-porous layer.

84. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more tubular fibres that are in porous or atresia, wherein oil is fed to the inboard or the outside of fiber.

85. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more tubular fibres that are in porous or atresia, wherein said fiber helically is reeled.

86. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more flat sheet materials that are in porous or atresia, wherein said flat sheet material helically is reeled.

87. according to the equipment of claim 67, wherein the semi-permeable membranes of flawless atresia is made up of the non-porous layer of the densification on one or more flat sheet materials that are in porous or atresia, wherein sealing coat is separated flat sheet material.

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